CN105367605B - Tetradentate platinum(II) complexes and their analogs cyclometallated with functionalized phenylcarbene ligands - Google Patents

Abstract

The present invention provides tetradentate platinum (II) complexes cyclometalated with functionalized phenylcarbene ligands and their analogs. The tetradentate platinum complexes of formula I and II are suitable for use as phosphorescent or delayed fluorescent and phosphorescent emitters in display and lighting applications.

Description

Tetradentate platinum(II) complexes and their analogs cyclometallated with functionalized phenylcarbene ligands

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Serial No. 62/028,562, entitled "TETRADENTATE PLATINUM(II) COMPLEXESCYCLOMETALATED WITH FUNCTIONALIZED PHENYL CARBENE LIGANDS AND THEIRANALOGUES," filed July 24, 2014, which is incorporated herein by reference in its entirety.

technical field

The present disclosure relates to tetradentate platinum(II) complexes for phosphorescent or delayed fluorescence and phosphorescent emitters in display and lighting applications, and in particular to phosphorescent or delayed fluorescence and phosphorescent tetradentate metal complexes with improved emission spectra compound.

Background technique

Compounds capable of absorbing and/or emitting light may be ideally suited for use in a wide variety of optical and electroluminescent devices including, for example, light absorbing devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices Devices, and devices capable of both light absorption and light emission and as markers for biological applications. Much research has been devoted to the discovery and optimization of organic and organometallic materials for use in optical and electroluminescent devices. In general, research in this area aims to achieve a number of goals, including improvements in absorption and emission efficiencies and improvements in device stability as well as improvements in processability.

Despite significant advances in research devoted to optical and optoelectronic materials (eg, red and green phosphorescent organometallic materials are commercially available and have been used as phosphors in organic light-emitting diodes (OLEDs), lighting, and advanced displays) , but many of the currently available materials exhibit a number of drawbacks including, among other things, poor processability, inefficient emission or absorption, and less than ideal stability.

Good blue light emitters are particularly rare, and one of the challenges is the stability of blue light devices. The choice of host material has an impact on the stability and efficiency of the device. The lowest triplet energy of the blue phosphor is very high compared to that of the red and green phosphors, which means that the lowest triplet energy of the host material for blue devices should be even higher. Therefore, one of the problems is that there are limited host materials for blue light devices. Therefore, there is a need for new materials that exhibit improved performance in optical emission and absorption applications.

SUMMARY OF THE INVENTION

designed and synthesized a series of cyclometalated tetradentate platinum(II) complexes with functionalized phenylcarbene ligands and their analogs (cyclized with functionalized phenylcarbene ligands and their analogs) Metallized tetradentate platinum(II) complex). These complexes offer improved color purity, enhanced operational stability, and reduced or eliminated potentially strong intermolecular interactions, and are suitable for use in luminescent labels, for use in organic light-emitting diodes (OLEDs) and Emitters for lighting applications, and photon downconverters.

Disclosed herein are complexes of Formula I and Formula II:

in:

Ar is five-membered heteroaryl, five-membered carbene, five-membered N-heterocyclic carbene, six-membered aryl, or six-membered heteroaryl,

或者

Each ^R1 is independently

or

Each of R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² is independently hydrogen, halogen, hydroxy, nitro , thiol; or substituted or unsubstituted: C ₁ -C ₄ alkyl, alkoxy, aryl, or amino, wherein R is absent when Ar is a five-membered ring,

X is O, S, S=O, O=S=O, Se, Se=O, O=Se=O, NR ^2a , PR ^2b , AsR ^2c , CR ^2d R ^2e , SiR ^2f R ^2g , or BR ^2h ,

Each of R ^2a , R ^2b , R ^2c , R ^2d , R ^2e , R ^2f , R ^2g , and R ^2h is independently a substituted or unsubstituted C ₁ -C ₄ alkyl or aryl,

Y is present or absent, and if present, Y is O, S, S=O, O=S=O, Se, Se=O, O=Se=O, NR ^3a , PR ^3b , AsR ^3c , CR ^3d R ^3e , SiR ^3f R ^3g , or BR ^3h , and

Each of R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g , and R ^3h is independently substituted or unsubstituted C ₁ -C ₄ alkyl or aryl.

唑、噻唑、吡啶等。在一些情况中，在相同环或者相邻环上的R、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、和R¹²中的任意两个结合(键合)在一起以形成稠环体系。例如，R和R²、R²和R⁴、或者R⁴和R⁶可结合从而与Ar形成稠环体系，例如苯并咪唑、苯并

唑、苯并噻唑、吲唑、喹啉、异喹啉、咪唑并[1,5-a]吡啶等。In some cases, Ar is pyrazole, imidazole,

azoles, thiazoles, pyridines, etc. In some cases, in R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² on the same ring or on adjacent rings Any two of are joined (bonded) together to form a fused ring system. For example, R and R ² , R ² and R ⁴ , or R ⁴ and R ⁶ can combine to form a fused ring system with Ar, such as benzimidazole, benzo

azole, benzothiazole, indazole, quinoline, isoquinoline, imidazo[1,5-a]pyridine, etc.

Also disclosed herein are compositions comprising one or more complexes disclosed herein, as well as devices such as OLEDs comprising one or more compounds or compositions disclosed herein.

Accordingly, specific embodiments have been described. Variations, modifications, and improvements to the described and other embodiments can be made based on what has been described and illustrated. Additionally, one or more features of one or more embodiments may be combined. The details of one or more implementations and various features and aspects are set forth in the accompanying drawings, the description, and the claims below.

Description of drawings

1 depicts a cross-sectional view of an exemplary organic light emitting device (OLED).

Figure 2 shows the photoluminescence spectra of Pt7O7-dipr at room temperature and 77K.

Detailed ways

The present disclosure may be understood more readily by reference to the following detailed description and the examples included therein.

Before the present complexes, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods unless otherwise specified, or that they are not limited to specific reagents unless otherwise specified, as these may of course vary. It will also be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing, example methods and materials are now described.

As used in this specification and the appended claims, the singular forms "a (a, an)" and "the (the)" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes a mixture of two or more components.

As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which said event or circumstance occurs and instances in which said event or circumstance occurs Circumstances in which an event or circumstance does not occur.

The components to be used in the preparation of the compositions described herein as well as the compositions themselves to be used in the methods disclosed herein are disclosed. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, collections, etc. of these materials are disclosed, notwithstanding the specific indication of each individual and collective combination and permutation of these compounds The items are not explicitly disclosed, but each is specifically designed and described herein. For example, if a particular compound is disclosed and discussed and the many variations that can be made to many molecules comprising the compound are discussed, the possible variations and every combination and permutation of the compounds are specifically designed unless specifically stated to the contrary. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and examples of combining molecules A-D are disclosed, each is individually and collectively even if not individually recited is designed, meaning that the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E and C-F are disclosed. Likewise, any subset or combination of these are also disclosed. Thus, for example, a subset of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application, including, but not limited to, steps in methods of making and using compositions. Thus, if there are multiple additional steps that can be performed, it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the described method.

As referred to herein, a linking atom or group may link two atoms, eg, a N atom and a C atom. Linking atoms or groups are disclosed herein as X, Y, Y ¹ , Y ² and/or Z in one aspect. The linking atom may optionally have other chemical moieties attached if valence permits. For example, in one aspect, once an oxygen is bonded to two groups (eg, N and/or C groups), the oxygen will not have any other chemical groups attached since the valences are satisfied. In another aspect, when carbon is the linking atom, two additional chemical moieties can be attached to the carbon. Suitable chemical moieties include amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl moieties.

The term "cyclic structure" or similar terms as used herein refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.

As used herein, the term "substituted" is intended to include all permissible substituents of organic compounds. In broad aspects, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents may be one or more and the same or different for suitable organic compounds. For purposes of this disclosure, a heteroatom, such as nitrogen, may have hydrogen substituents and/or any permissible substituents of the organic compounds described herein that satisfy the valences of the heteroatoms. This disclosure is not intended to be limited in any way by the permissible substituents of organic compounds. Furthermore, the terms "substituted" or "substituted by" include the implied condition that such substitution is based on the permissible valences of the substituted atoms and substituents, and that the substitution results in a stable compound, eg, that does not spontaneously undergo a transformation ( Compounds such as by rearrangement, cyclization, elimination, etc.). It is also contemplated that, in some aspects, unless expressly stated to the contrary, individual substituents may be further optionally substituted (ie, further substituted or unsubstituted).

In defining various terms, "X" and "Y" are used herein as general symbols to refer to various specific substituents. These symbols can be any substituents, not limited to those disclosed herein, and when they are defined as some substituents in one context, they can be defined as some other substituents in another context.

The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1-24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl base, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. Alkyl groups can be cyclic or acyclic. Alkyl groups can be branched or unbranched. Alkyl groups can also be substituted or unsubstituted. For example, an alkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen (halide, halide), hydroxyl, nitro, silyl, sulfo-oxo, or thiol. A "lower alkyl" group is an alkyl group containing from one to six (eg, one to four) carbon atoms.

Throughout the specification, "alkyl" is used broadly to refer to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specified herein by identifying the specific substituent on the alkyl group mentioned. For example, the term "haloalkyl" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halogens such as fluorine, chlorine, bromine, or iodine. The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, etc., as described below. When "alkyl" is used in one context and a specific term such as "alkyl alcohol" is used in another context, it is not intended to imply that the term "alkyl" does not also refer to a specific term such as "alkyl alcohol" Wait.

This practice can also be used for other groups described herein. That is, although terms such as "cycloalkyl" refer to both unsubstituted and substituted cycloalkyl moieties, substituted moieties may otherwise be specifically identified herein; for example, a particular substituted cycloalkyl may be referred to as For example "alkylcycloalkyl". Similarly, substituted alkoxy groups can be specifically referred to as, for example, "halogenated alkoxy groups," and specific substituted alkenyl groups can be, for example, "alkenyl alcohols," and the like. Again, the practice of using general terms such as "cycloalkyl" as well as specific terms such as "alkylcycloalkyl" is not intended to imply that the general term does not also include the specific term.

The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above, and is included within the meaning of the term "cycloalkyl" wherein at least one of the carbon atoms of the ring is replaced by a heteroatom such as , but not limited to nitrogen, oxygen, sulfur, or phosphorus. Cycloalkyl and heterocycloalkyl can be substituted or unsubstituted. Cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, Hydroxyl, nitro, silyl, thio-oxo, or thiol.

The term "polyolefin group" as used herein is a group having two or more _CH2 groups attached to each other. The polyolefin group can be represented by the formula -( _CH2 ) _a- , wherein "a" is an integer from 2-500.

The terms "alkoxy" and "alkoxy," as used herein, refer to an alkyl or cycloalkyl group bonded through an ether linkage; ie, an "alkoxy" group can be defined as -OA ¹ , where A ¹ is alkyl or cycloalkyl as defined above. "Alkoxy" also includes polymers of alkoxy groups as just described; that is, the alkoxy may be a polyether, such as -OA ¹ -OA ² or -OA ¹ -(OA ² ) _a -OA ³ , wherein "a" is an integer from 1 to 200 and A ¹ , A ² , and A ³ are alkyl and/or cycloalkyl groups.

As used herein, "alkenyl" is a hydrocarbyl group of 2-24 carbon atoms having a structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (A ¹ A ² )C=C(A ³ A ⁴ ) are intended to include both E and Z isomers. This can be inferred from the structural formulas herein in which the asymmetric olefin is present, or it can be explicitly indicated by the bond symbol C=C. Alkenyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkyne as described herein group, aryl, heteroaryl, aldehyde, amino, carboxylate, ester, ether, halogen, hydroxyl, keto, azido, nitro, silyl, thio-oxo, or thiol base.

The term "cycloalkenyl" as used herein is a non-aromatic carbon-based ring consisting of at least three carbon atoms and containing at least one carbon-carbon double bond, ie, C=C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl" is a class of cycloalkenyl groups as defined above and is included within the meaning of the term "cycloalkenyl" wherein at least one of the carbon atoms of the ring is replaced by a heteroatom such as , but not limited to nitrogen, oxygen, sulfur or phosphorus. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. Cycloalkenyl and heterocycloalkenyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, Alkynyl, Cycloalkynyl, Aryl, Heteroaryl, Aldehyde, Amino, Carboxylic, Ester, Ether, Halogen, Hydroxy, Keto, Azido, Nitro, Silyl, Sulfur-Oxygen Generation, or thiol group.

The term "alkynyl" as used herein is a hydrocarbyl group of 2-24 carbon atoms having a structural formula containing at least one carbon-carbon triple bond. Alkynyl groups can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, Alkynyl, Cycloalkynyl, Aryl, Heteroaryl, Aldehyde, Amino, Carboxylic, Ester, Ether, Halogen, Hydroxy, Keto, Azido, Nitro, Silyl, Sulfur-Oxygen Generation, or thiol group.

The term "cycloalkynyl" as used herein is a non-aromatic carbon-based ring consisting of at least seven carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is a class of cycloalkynyl groups as defined above and is included within the meaning of the term "cycloalkynyl" wherein at least one of the carbon atoms of the ring is replaced by a heteroatom such as , but not limited to nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl groups can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, Alkynyl, Cycloalkynyl, Aryl, Heteroaryl, Aldehyde, Amino, Carboxylic, Ester, Ether, Halogen, Hydroxy, Keto, Azido, Nitro, Silyl, Sulfur-Oxygen Generation, or thiol group.

The term "aryl" as used herein is a group containing any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group having at least one heteroatom introduced into the ring of the aromatic group . Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term "non-heteroaryl" is also included within the scope of the term "aryl," which defines a group that includes an aromatic group that does not contain a heteroatom. Aryl groups can be substituted or unsubstituted. Aryl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl as described herein , aryl, heteroaryl, aldehyde, amino, carboxylate, ester, ether, halogen, hydroxyl, ketone, azide, nitro, silyl, thio-oxo, or thiol . The term "biaryl" is a special type of aryl group and is included within the definition of the term "aryl". Biaryl refers to two aryl groups joined together via a fused ring structure (as in naphthalene), or via one or more carbon-carbon bonds (as in biphenyl).

The term "aldehyde group" as used herein is represented by the formula -C(O)H. Throughout this specification, "C(O)" is a shorthand notation for carbonyl, ie, C=O.

^The term "amino" or "amino" as used herein is represented by the ^{formula -NA1A2} , wherein A1 and A2 may independently be ^hydrogen or alkyl, cycloalkyl, alkenyl, Cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.

The term "alkylamino" as used herein is represented by the formula -NH(-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl)amino, (tert-butyl)amino, Amylamino, isopentylamino, (tert-amyl)amino, hexylamino and the like.

The term "dialkylamino" as used herein is represented by the formula -N(-alkyl) ₂ , wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di(sec-butyl)amino, Di(tert-butyl)amino, dipentylamino, diisoamylamino, di(tert-amyl)amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propane amino, N-ethyl-N-propylamino, etc.

The term "carboxylate" as used herein is represented by the formula -C(O)OH.

The term "ester group" as used herein is represented by the formula -OC(O)A ¹ or -C(O)OA ¹ , wherein A ¹ can be an alkyl, cycloalkyl, alkenyl, cyclo, as described herein Alkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl. The term "polyester-based" as used herein is represented by the formula -(A ¹ O(O)CA ² -C(O)O) _a - or -(A ¹ O(O)CA ² -OC(O)) _a - means where ^A and ^A can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein and "a" is 1 -500 integer. "Polyester group" is a term used to describe a group produced by a reaction between a compound having at least two carboxylic acid groups and a compound having at least two hydroxyl groups.

^The term "ether" as used herein is represented by the ^{formula A1OA2} , wherein A1 and ^A2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkyne as described herein aryl, aryl or heteroaryl. The term "polyether group" as used herein is represented by the formula -(A ¹ OA ² O) _a -, wherein A ¹ and A ² may independently be alkyl, cycloalkyl, alkenyl, cyclic as described herein alkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl and "a" is an integer from 1-500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.

The term "polymeric" includes polyolefins, polyethers, polyesters, and other groups having repeating units such as, but not limited to, -(CH2O) _n - _CH3 , _- ( _CH2CH2O ) _{n - CH3} , -[CH ₂ CH(CH ₃ )] _n -CH ₃ , -[CH ₂ CH(COOCH ₃ )] _n -CH ₃ , -[CH ₂ CH(COOCH ₂ CH ₃ )] _n -CH ₃ , and - [CH2CH( ^COOtBu )] _{n- CH3 ,} where n is an integer (eg, n>1 or n>2).

The term "halogen" as used herein refers to the halogens fluorine, chlorine, bromine and iodine.

唑、吗啉、

唑、

唑(

二唑)(包括1,2,3-

二唑、1,2,5-

二唑和1,3,4-

二唑)、哌嗪、哌啶、吡嗪、吡唑、哒嗪、吡啶、嘧啶、吡咯、吡咯烷、四氢呋喃、四氢吡喃、四嗪(包括1,2,4,5-四嗪)、四唑(包括1,2,3,4-四唑和1,2,4,5-四唑)、噻二唑(包括1,2,3-噻二唑、1,2,5-噻二唑和1,3,4-噻二唑)、噻唑、噻吩、三嗪(包括1,3,5-三嗪和1,2,4-三嗪)、三唑(包括1,2,3-三唑、1,3,4-三唑)等。The term "heterocyclyl" as used herein refers to monocyclic and polycyclic non-aromatic ring systems and the term "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems: wherein the ring members at least one of which is different from carbon. The term includes azetidine, dioxane, furan, imidazole, isothiazole, iso

azole, morpholine,

azole,

azole (

oxadiazole) (including 1,2,3-

oxadiazole, 1,2,5-

oxadiazole and 1,3,4-

oxadiazole), piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrazine (including 1,2,4,5-tetrazine) , tetrazole (including 1,2,3,4-tetrazole and 1,2,4,5-tetrazole), thiadiazole (including 1,2,3-thiadiazole, 1,2,5-thiadiazole oxadiazole and 1,3,4-thiadiazole), thiazole, thiophene, triazine (including 1,3,5-triazine and 1,2,4-triazine), triazole (including 1,2,3 - triazole, 1,3,4-triazole) and the like.

The term "hydroxyl" as used herein is represented by the formula -OH.

^The term "ketone" as used herein is represented by the ^{formula A1C (} O)A2, wherein A1 and A2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, cycloalkynyl, aryl or heteroaryl.

The term "azido" as used herein is represented by the formula -N ₃ .

The term "nitro" as used herein is represented by the formula -NO ₂ .

The term "nitrile group" as used herein is represented by the formula -CN.

The term "silyl" as used herein is represented by the formula -SiA ¹ A ² A ³ , wherein A ¹ , A ² and A ³ can independently be hydrogen or alkyl, cycloalkyl, alkane as described herein Oxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.

The term "thio-oxo" as used herein is represented by the formula -S(O)A ¹ , -S(O) ₂ A ¹ , -OS(O) ₂ A ¹ , or -OS(O) ₂ OA ¹ , where A ¹ can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout this specification, "S(O)" is a shorthand notation for S=O. The term "sulfonyl" as used herein refers to ^a thio-oxo group represented by the _formula -S(O)2A1, wherein A1 can be hydrogen or ^an alkyl, cycloalkyl as described herein , alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl. ^The term "sulfone" as used herein is represented by the ^{formula A1S} (O ⁾ _2A2 , wherein A1 and A2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl as described herein , alkynyl, cycloalkynyl, aryl or heteroaryl. ^The term "sulfoxide" as used herein is represented by the ^{formula A1S} (O ⁾ A2, wherein A1 and A2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl as described herein , alkynyl, cycloalkynyl, aryl or heteroaryl.

The term "thiol" as used herein is represented by the formula -SH.

As used herein, "R1", "R2", " ^R3 ", " ^Rn ", wherein ⁿ is an integer, may independently have one or more of the above ^- listed groups. For example, if R1 is ^a straight chain alkyl group, one of the hydrogen atoms of the alkyl group may be optionally substituted with hydroxy, alkoxy, alkyl, halogen, and the like. Depending on the group chosen, the first group can be incorporated into the second group, or alternatively, the first group can be pendant (ie, attached) to the second group. For example, for the phrase "an alkyl group containing an amino group," an amino group can be incorporated into the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is intercalated or attached to the second group.

The compounds described herein may contain "optionally substituted" moieties. In general, the term "substituted", whether or not preceded by the term "optionally", means that one or more hydrogen atoms of the specified moiety have been replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be selected from the specified group When more than one substituent of a group is substituted, the substituents may be the same or different at each position. Combinations of substituents contemplated by the present invention are preferably those that result in the formation of stable or chemically feasible compounds. It is also contemplated that, in some aspects, individual substituents may be further optionally substituted (ie, further substituted or unsubstituted) unless explicitly stated to the contrary.

In some aspects, the structure of the compound can be represented by the formula:

It is understood to be equivalent to:

where n is typically an integer. That is, R ⁿ is understood to represent five independent substituents R ^n(a) , R ^n(b) , R ^n(c) , R ^n(d) , R ^{n (e)} . "Independent substituent" means that each R substituent may be independently defined. For example, if in one instance ^Rn(a) is halogen, then Rn ^(b) in that instance is not necessarily halogen.

R1, R2, ^R3 , ^R4 , ^R5 , ^R6 , ^etc. are mentioned several times in the chemical structures and moieties disclosed and described herein ^. Any description of R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , etc. in this specification may apply to listing R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , any structure or moiety of R ⁶ etc.

Optoelectronic devices utilizing organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have potential relative to inorganic devices due to cost advantages. Furthermore, the intrinsic properties of organic materials, such as their flexibility, can make them well suited for specific applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting devices (organic light emitting diodes) (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength of light emitted by the organic light-emitting layer can be easily adjusted, usually using suitable dopants.

Excitons decay from a singlet excited state to a ground state to produce rapid luminescence, which is fluorescence. The excitons decay from the triplet excited state to the ground state to produce luminescence, which is phosphorescence. Because the strong spin-orbit coupling of heavy metal atoms highly effectively enhances intersystem crossing (ISC) between singlet and triplet excited states, phosphorescent metal complexes such as platinum complexes have been shown to trap singlet and triplet states. Potential for triplet excitons to achieve 100% internal quantum efficiency. Therefore, phosphorescent metal complexes are good candidates as dopants in the emission layer of organic light-emitting devices (OLEDs) and have received a lot of attention in both academic and industrial fields.

However, blue electroluminescent devices remain by far the most challenging area of this technology, due at least in part to the instability of blue light devices. It is generally understood that the choice of host material is a factor in the stability of blue light devices. However, the lowest triplet excited state (T ₁ ) energy of blue phosphors is high, which generally means that the lowest triplet excited state (T ₁ ) energy of the host material of the blue device should be even higher. This leads to difficulties in the development of host materials for blue light devices.

The present disclosure provides a material design route by introducing carbon-based groups (C, Si, Ge) bridging the ligands of the metal complexes. As described herein, it was found that the photoluminescence spectra of carbon-bridged Pt complexes have a significant blue shift compared to nitrogen-bridged Pt complexes with the same emissive groups. It has also been found that the chemical structure of the emitting luminophore and ligand can be altered, as well as the metal can be altered to tune the singlet and triplet energies of the metal complex, which can all affect the optical properties of the complex.

The metal complexes described herein can be tailored or tailored to specific applications facilitated by specific emission or absorption properties. The optical properties of the metal complexes in the present disclosure can be tuned by changing the structure of the ligand surrounding the metal center or by changing the structure of the fluorophore on the ligand. For example, metal complexes with ligands possessing electron-donating or electron-withdrawing substituents can often exhibit different optical properties, including emission and absorption spectra. The color of the metal complex can be adjusted by changing the conjugated groups on the ligand and fluorophore.

The emission of such complexes can be tuned, for example, from the ultraviolet to the near-infrared by, for example, changing the ligand or fluorophore structure. A fluorophore is a group of atoms in an organic molecule that can absorb energy to produce one or more singlet excited states. One or more singlet excitons rapidly decay to produce rapid luminescence. In one aspect, the complex can provide emission over a substantial portion of the visible spectrum. In a specific example, the complexes described herein can emit light in the range of about 400 nm to about 700 nm. In another aspect, the complexes have improved stability and efficiency relative to traditional light-emitting complexes. In yet another aspect, the complexes may be useful as labels in, for example, biological applications, anticancer agents, emitters in organic light emitting diodes (OLEDs), or combinations thereof. In another aspect, the complexes can be useful in light emitting devices, eg, compact fluorescent lamps (CFLs), light emitting diodes (LEDs), incandescent lamps, and combinations thereof.

Disclosed herein are platinum compounds, compound complexes, or complexes. The terms compound, compound complex, and complex are used interchangeably herein. In one aspect, the compounds disclosed herein have neutral charge.

The compounds disclosed herein can exhibit desirable properties and possess emission and/or absorption spectra that can be tuned via the selection of suitable ligands. In another aspect, any one or more of the compounds, structures, or portions thereof specifically recited herein may be excluded.

The compounds disclosed herein are suitable for use in a wide variety of optical and optoelectronic devices, including, but not limited to, light absorbing devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices, or both capable of Light absorption also enables light emission and devices as markers for biological applications.

As briefly described above, the disclosed compounds are platinum complexes. In one aspect, the compounds disclosed herein can be used as host materials for OLED applications such as full color displays.

The compounds disclosed herein can be useful in a variety of applications. As light-emitting materials, the compounds may be useful in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.

In another aspect, the compounds can provide improved efficiency and/or improved operating lifetime in lighting devices, such as organic light emitting devices, as compared to conventional materials.

The compounds described herein can be made using a variety of methods including, but not limited to, those recited in the Examples.

The compounds disclosed herein include delayed fluorescent emitters, phosphorescent emitters, or combinations thereof. In one aspect, the compounds disclosed herein are delayed fluorescence emitters. In another aspect, the compounds disclosed herein are phosphorescent emitters. In yet another aspect, the compounds disclosed herein are both delayed fluorescent emitters and phosphorescent emitters.

Disclosed herein are complexes of Formula I and Formula II:

in:

Ar is five-membered heteroaryl, five-membered carbene, five-membered N-heterocyclic carbene, six-membered aryl, or six-membered heteroaryl,

或者

Each ^R1 is independently

or

Each of R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² is independently hydrogen, halogen, hydroxy, nitro , thiol; substituted or unsubstituted: C ₁ -C ₄ alkyl, alkoxy, aryl, or amino, wherein R is absent when Ar is a five-membered ring,

X is O, S, S=O, O=S=O, Se, Se=O, O=Se=O, NR ^2a , PR ^2b , AsR ^2c , CR ^2d R ^2e , SiR ^2f R ^2g , or BR ^2h ,

Each of R ^2a , R ^2b , R ^2c , R ^2d , R ^2e , R ^2f , R ^2g , and R ^2h is independently a substituted or unsubstituted C ₁ -C ₄ alkyl or aryl,

Y is present or absent, and if present, Y is O, S, S=O, O=S=O, Se, Se=O, O=Se=O, NR ^3a , PR ^3b , AsR ^3c , CR ^3d R ^3e , SiR ^3f R ^3g , or BR ^3h , and

Each of R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g , and R ^3h is independently substituted or unsubstituted C ₁ -C ₄ alkyl or aryl.

唑、噻唑、吡啶等。在一些情况中，在相同环或者相邻环上的R、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、和R¹²中的任意两个结合在一起以形成稠环体系。例如，R和R²、R²和R⁴、或者R⁴和R⁶可结合以与Ar形成稠环体系，例如苯并咪唑、苯并

唑、苯并噻唑、吲唑、喹啉、异喹啉、咪唑并[1,5-a]吡啶等。In some cases, Ar is pyrazole, imidazole,

azoles, thiazoles, pyridines, etc. In some cases, in R, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² on the same ring or on adjacent rings Any two of them are combined together to form a fused ring system. For example, R and R ² , R ² and R ⁴ , or R ⁴ and R ⁶ can be combined to form a fused ring system with Ar, such as benzimidazole, benzo

azole, benzothiazole, indazole, quinoline, isoquinoline, imidazo[1,5-a]pyridine, etc.

In some cases, X is directly linked to R ¹⁰ or R ¹¹ . In some cases, Y is directly linked to R ⁶ or R ⁸ .

基(mesityl)”；“Dipp”是指“二异丙基苯基”；“Np”是指“新戊基”；和“Cy”是指“环己基”。Metal complexes in the present disclosure include one or more of the following structures. The metal complexes in the present disclosure may also include other structures or portions thereof not specifically described herein, and the present disclosure is not intended to be limited to those structures or portions thereof specifically described. In the structures below, "Ad" refers to "adamantyl";"Mes" refers to "

"Dipp" means "diisopropylphenyl";"Np" means "neopentyl"; and "Cy" means "cyclohexyl".

Also disclosed herein are devices comprising one or more of the complexes disclosed herein.

The complexes disclosed herein are suitable for use in a wide variety of devices, including, for example, optical and optoelectronic devices, including, for example, light absorbing devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices, or Devices capable of both light absorption and light emission and as markers for biological applications.

Also disclosed herein are devices comprising one or more of the complexes disclosed herein.

The complexes disclosed herein are suitable for use in a wide variety of devices, including, for example, optical and optoelectronic devices, including, for example, light absorbing devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices, or Devices capable of both light absorption and light emission and as markers for biological applications.

The complexes described herein can be used in OLEDs. FIG. 1 depicts a cross-sectional view of OLED 100 . OLED 100 includes substrate 102 , anode 104 , hole transport material (HTL) 106 , light treatment material 108 , electron transport material (ETL) 110 , and metal cathode layer 112 . Anode 104 is typically a transparent material such as indium tin oxide. The light treatment material 108 may be an emissive material (EML) comprising an emitter and a host.

In various aspects, any of the one or more layers depicted in FIG. 1 can comprise indium tin oxide (ITO), poly(3,4-ethylenedioxythiophene) (PEDOT), polysulfobenzene Ethylene (PSS), N,N'-di-1-naphthyl-N,N-diphenyl-1,1'-biphenyl-4,4'-diamine (NPD), 1,1-bis( (Bis-4-Tolylamino)phenyl)cyclohexane (TAPC), 2,6-bis(N-carbazolyl)pyridine (mCpy), 2,8-bis(diphenylphosphoryl)diphenyl thiophene (PO15), LiF, Al, or a combination thereof.

The light treatment material 108 may include one or more complexes of the present disclosure and a host material or no host material. The host material may be any suitable known host material. The emission color of the OLED is determined by the emission energy (optical energy gap) of the light processing material 108, which can be tuned by adjusting the electronic structure of the luminescent complex and/or host material. Both the hole transport material in HTL layer 106 and the electron transport material in ETL layer 110 may comprise any suitable known hole transporter.

The complexes described herein can exhibit phosphorescence. Phosphorescent OLEDs (ie, OLEDs with phosphorescent emitters) typically have higher device efficiencies than other OLEDs, such as fluorescent OLEDs. Light emitting devices based on electrophosphorescent emitters are described in more detail in WO2000/070655 to Baldo et al., which is incorporated herein for its teachings on OLEDs and in particular phosphorescent OLEDs.

Example

The following examples are presented to provide those of ordinary skill in the art with a complete disclosure and description of how to make and evaluate the compounds, compositions, articles, devices and/or methods described herein, and are intended to be exemplary only and is not intended to limit the scope. Although efforts have been made to ensure accuracy with respect to numerical values (eg, amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise stated, parts are parts by weight, temperature is in °C or at ambient temperature, and pressure is at or near atmospheric.

Various methods for the preparation of the compounds described herein are described in the Examples. These methods are provided to illustrate various methods of preparation, but are not intended to limit any of the methods described herein. Accordingly, one skilled in the art to which this disclosure pertains can readily modify the described methods or utilize different methods to prepare one or more of the compounds described herein. The following aspects are exemplary only, and are not intended to be limiting. The ranges, temperatures, catalysts, concentrations, reactant compositions, and other process conditions may vary, and for desired complexes, those skilled in the art to which this disclosure pertains can readily Choose appropriate reactants and conditions.

¹ H spectra were recorded at 400 MHz and ¹³ C NMR spectra were recorded at 100 MHz in CDCl ₃ or DMSO-d ₆ solution on a Varian Liquid State NMR instrument and chemical shifts were referenced to residual protonated solvent. If _CDCl3 was used as solvent, ^1H NMR spectra were recorded using tetramethylsilane (δ=0.00 ppm) as internal standard; ^13C NMR spectra were recorded using _CDCl3 (δ=77.00 ppm) as internal standard. If DMSO-d ₆ was used as solvent, ¹ H NMR spectra were recorded using residual H ₂ O (δ = 3.33 ppm) as internal standard; ¹³ C NMR spectra were recorded using DMSO-d ₆ (δ = 39.52 ppm) as internal standard spectrum. The following abbreviations (or combinations thereof) are used to illustrate the multiplicity of1H NMR: s ⁼ single, d=double, t=triple, q=quad, p=quintet, m=multiple, br=broad.

Exemplary synthetic methods for the complexes disclosed herein are described with reference to Scheme 1 below for Pt7O7-dipr.

plan 1

To the oven dried flask was added the ligand for Pt7O7 _- dipr (610 mg, 0.9 mmol), _{K2PtCl4 (} 392 mg, 0.945 mmol), and n-Bu4NBr (29 mg, 0.09 mmol). The flask was evacuated and backfilled with _N2 , then HOAc (45 mL, 0.02M) was added under the protection of _N2 . The mixture was then heated at 120°C for 3 days. The resulting mixture was cooled to room temperature and concentrated under reduced pressure. Purification by flash column chromatography on silica gel (DCM/hexane = 1/1 to 3/1) provided Pt7O7-dipr (99 mg, 19% yield) as a pale yellow solid. ¹ H NMR (DMSO-d ₆ , 400MHz): δ 8.04 (d, J=2.0 Hz, 2H), 7.65 (d, J=2.0 Hz, 2H), 7.20 (d, J=7.4 Hz, 2H), 7.11 (t, J=7.8 Hz, 2H), 6.96-6.85 (m, 2H), 4.78 (sept, J=6.6 Hz, 2H), 1.47 (d, J=6.6 Hz, 12H). The photoluminescence spectra of Pt7O7-dipr at room temperature and 77 K are shown in Fig. 2.

The complexes described herein are suitable as emitters for light-emitting devices such as OLEDs (eg, for full-color displays and lighting applications).

Further modifications and alternative embodiments of various aspects will be apparent to those skilled in the art in view of this specification. Accordingly, this specification is to be construed as illustrative only. It is to be understood that the forms shown and described herein are to be considered as examples of embodiments. Elements and materials may be substituted for those illustrated and described herein, components and processes may be reversed, and some features may be utilized independently, all of which will be apparent to those skilled in the art having the benefit of this description of. Changes may be made in elements described herein without departing from the spirit and scope as set forth in the following claims.

Claims (16)

1. A complex represented by formula I:

in: Each ^R1 is independently

Each of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is independently hydrogen, halogen, unsubstituted C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, or C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy substituted by C ₁ -C ₄ alkyl or halogen, X is O, S or Se. 2. The complex of claim 1, wherein: Each ^R1 is independently

3. The complex of claim 1, wherein each of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is independently hydrogen or hydrogen Substituted C ₁ -C ₄ alkyl. 4. The complex of claim 1, wherein X is O or S. 5. The complex of claim 1, wherein: Each ^R1 is independently

Each of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is independently hydrogen or unsubstituted C ₁ -C ₄ alkyl; and X is O. 6. The complex of claim 1 having one of the following chemical structures:

7. The complex of claim 1 having the following chemical structure:

8. The complex of claim 1, which is:

9. Use of a complex according to any of claims 1 to 8 as a phosphorescent emitter. 10. A method of preparing the complex of any one of claims 1-8, the method comprising: combining the ligand with a platinum salt, a bromine-containing compound, and acetic acid to obtain a mixture; heating the mixture; and The mixture was cooled to room temperature. 11. The method of claim ₁₀ , wherein the platinum salt is _K2PtCl4 . 12. The method of claim 10 or claim 11, wherein the bromine-containing compound is n _- Bu4NBr. 13. A device comprising the complex of any of claims 1-8. 14. The device of claim 13, wherein the device is a light emitting device. 15. The device of claim 14, wherein the device is an organic light emitting diode. 16. The device of claim 14, wherein the device is a full color display.

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